Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks
Covalent organic frameworks (COFs) have emerged as promising semiconducting materials for photocatalytic applications due to their large surface area, high crystallinity, and vast synthetic tunability. This is especially noticeable in the context of photocatalytic water splitting, where many COFs ha...
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| منشور في: |
2025
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| _version_ | 1852019682609987584 |
|---|---|
| author | Stefan Trenker (21477936) |
| author2 | Hugo A. Vignolo-Gonzalez (21477939) Andrés Rodríguez-Camargo (12765804) Liang Yao (823113) Martijn A. Zwijnenburg (1301334) Bettina V. Lotsch (1467520) |
| author2_role | author author author author author |
| author_facet | Stefan Trenker (21477936) Hugo A. Vignolo-Gonzalez (21477939) Andrés Rodríguez-Camargo (12765804) Liang Yao (823113) Martijn A. Zwijnenburg (1301334) Bettina V. Lotsch (1467520) |
| author_role | author |
| dc.creator.none.fl_str_mv | Stefan Trenker (21477936) Hugo A. Vignolo-Gonzalez (21477939) Andrés Rodríguez-Camargo (12765804) Liang Yao (823113) Martijn A. Zwijnenburg (1301334) Bettina V. Lotsch (1467520) |
| dc.date.none.fl_str_mv | 2025-06-04T06:29:30Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.chemmater.5c00804.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/dataset/Identifying_Bottlenecks_in_the_Photocatalytic_Oxygen_Evolution_Reaction_with_Covalent_Organic_Frameworks/29233575 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biochemistry Medicine Molecular Biology Evolutionary Biology Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified vast synthetic tunability using computational methods sandwich complex onto retained catalytic activity promising semiconducting materials large surface area hydrogen evolution half electrocatalytic tests indicate photocatalytic applications due photocatalytic water splitting sacrificial electron acceptor oxygen evolution cocatalyst ir ( iii careful control experiments control experiments subsequent photocatalytic water oxidation targeted cocatalyst evolve oxygen careful evaluation work demonstrates use heterogenization trace back reports focus pitfalls associated missing performance limited insight kinetic limitations identifying bottlenecks high crystallinity especially noticeable detailed role cof photocatalysts cobalt species bpy cof based cof anchored cp |
| dc.title.none.fl_str_mv | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| dc.type.none.fl_str_mv | Dataset info:eu-repo/semantics/publishedVersion dataset |
| description | Covalent organic frameworks (COFs) have emerged as promising semiconducting materials for photocatalytic applications due to their large surface area, high crystallinity, and vast synthetic tunability. This is especially noticeable in the context of photocatalytic water splitting, where many COFs have been employed for the hydrogen evolution half-reaction. There, sacrificial reagents typically replace the kinetically demanding oxygen evolution half-reaction. On the contrary, only few reports focus on (sacrificial) water oxidation with COF photocatalysts. In most of these cases, cobalt species are employed as oxygen evolution cocatalyst, often with limited insight into their structure and detailed role in the catalysis. Herein, we use heterogenization of a molecularly defined iridium half-sandwich complex onto a bipyridine-based COF (Ir@TAPB-BPY COF) and provide detailed structural insights ensuring the integrity of the targeted cocatalyst. First, we demonstrate the retained catalytic activity of the anchored Cp*Ir(III) motifs in chemical water oxidation experiments. In contrast, subsequent photocatalytic and electrocatalytic tests indicate that Ir@TAPB-BPY COF does not evolve oxygen and that careful control experiments have to be conducted in order to avoid false positive results, caused for example by the sacrificial electron acceptor. Using computational methods, we trace back the missing performance to thermodynamic and kinetic limitations of the employed systems. This work demonstrates the pitfalls associated with low-performing oxygen evolution photocatalysts as well as the indispensability of control experiments and their careful evaluation. |
| eu_rights_str_mv | openAccess |
| id | Manara_3774bc8a27ccd777f9df7cf0e1a0be4e |
| identifier_str_mv | 10.1021/acs.chemmater.5c00804.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/29233575 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic FrameworksStefan Trenker (21477936)Hugo A. Vignolo-Gonzalez (21477939)Andrés Rodríguez-Camargo (12765804)Liang Yao (823113)Martijn A. Zwijnenburg (1301334)Bettina V. Lotsch (1467520)BiochemistryMedicineMolecular BiologyEvolutionary BiologyComputational BiologyEnvironmental Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedvast synthetic tunabilityusing computational methodssandwich complex ontoretained catalytic activitypromising semiconducting materialslarge surface areahydrogen evolution halfelectrocatalytic tests indicatephotocatalytic applications duephotocatalytic water splittingsacrificial electron acceptoroxygen evolution cocatalystir ( iiicareful control experimentscontrol experimentssubsequent photocatalyticwater oxidationtargeted cocatalystevolve oxygencareful evaluationwork demonstratesuse heterogenizationtrace backreports focuspitfalls associatedmissing performancelimited insightkinetic limitationsidentifying bottleneckshigh crystallinityespecially noticeabledetailed rolecof photocatalystscobalt speciesbpy cofbased cofanchored cpCovalent organic frameworks (COFs) have emerged as promising semiconducting materials for photocatalytic applications due to their large surface area, high crystallinity, and vast synthetic tunability. This is especially noticeable in the context of photocatalytic water splitting, where many COFs have been employed for the hydrogen evolution half-reaction. There, sacrificial reagents typically replace the kinetically demanding oxygen evolution half-reaction. On the contrary, only few reports focus on (sacrificial) water oxidation with COF photocatalysts. In most of these cases, cobalt species are employed as oxygen evolution cocatalyst, often with limited insight into their structure and detailed role in the catalysis. Herein, we use heterogenization of a molecularly defined iridium half-sandwich complex onto a bipyridine-based COF (Ir@TAPB-BPY COF) and provide detailed structural insights ensuring the integrity of the targeted cocatalyst. First, we demonstrate the retained catalytic activity of the anchored Cp*Ir(III) motifs in chemical water oxidation experiments. In contrast, subsequent photocatalytic and electrocatalytic tests indicate that Ir@TAPB-BPY COF does not evolve oxygen and that careful control experiments have to be conducted in order to avoid false positive results, caused for example by the sacrificial electron acceptor. Using computational methods, we trace back the missing performance to thermodynamic and kinetic limitations of the employed systems. This work demonstrates the pitfalls associated with low-performing oxygen evolution photocatalysts as well as the indispensability of control experiments and their careful evaluation.2025-06-04T06:29:30ZDatasetinfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.chemmater.5c00804.s002https://figshare.com/articles/dataset/Identifying_Bottlenecks_in_the_Photocatalytic_Oxygen_Evolution_Reaction_with_Covalent_Organic_Frameworks/29233575CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/292335752025-06-04T06:29:30Z |
| spellingShingle | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks Stefan Trenker (21477936) Biochemistry Medicine Molecular Biology Evolutionary Biology Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified vast synthetic tunability using computational methods sandwich complex onto retained catalytic activity promising semiconducting materials large surface area hydrogen evolution half electrocatalytic tests indicate photocatalytic applications due photocatalytic water splitting sacrificial electron acceptor oxygen evolution cocatalyst ir ( iii careful control experiments control experiments subsequent photocatalytic water oxidation targeted cocatalyst evolve oxygen careful evaluation work demonstrates use heterogenization trace back reports focus pitfalls associated missing performance limited insight kinetic limitations identifying bottlenecks high crystallinity especially noticeable detailed role cof photocatalysts cobalt species bpy cof based cof anchored cp |
| status_str | publishedVersion |
| title | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| title_full | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| title_fullStr | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| title_full_unstemmed | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| title_short | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| title_sort | Identifying Bottlenecks in the Photocatalytic Oxygen Evolution Reaction with Covalent Organic Frameworks |
| topic | Biochemistry Medicine Molecular Biology Evolutionary Biology Computational Biology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified vast synthetic tunability using computational methods sandwich complex onto retained catalytic activity promising semiconducting materials large surface area hydrogen evolution half electrocatalytic tests indicate photocatalytic applications due photocatalytic water splitting sacrificial electron acceptor oxygen evolution cocatalyst ir ( iii careful control experiments control experiments subsequent photocatalytic water oxidation targeted cocatalyst evolve oxygen careful evaluation work demonstrates use heterogenization trace back reports focus pitfalls associated missing performance limited insight kinetic limitations identifying bottlenecks high crystallinity especially noticeable detailed role cof photocatalysts cobalt species bpy cof based cof anchored cp |