A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption
- Publication type:
- Journal article
- Metadata:
-
- Autoren
- Dariusz Mitoraj
- Igor Krivtsov
- Chunyu Li
- Ashwene Rajagopal
- Changbin Im
- Christiane Adler
- Kerstin Koble
- Olena Khainakova
- Julian Hniopek
- Christof Neumann
- Andrey Turchanin
- Ivan da Silva
- Michael Schmitt
- Robert Leiter
- Tibor Lehnert
- Jurgen Popp
- Ute Kaiser
- Timo Jacob
- Carsten Streb
- Benjamin Dietzek
- Radim Beranek
- Autoren-URL
- https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000709252200001&DestLinkType=FullRecord&DestApp=WOS_CPL
- DOI
- 10.1002/chem.202102945
- eISSN
- 1521-3765
- Externe Identifier
- Clarivate Analytics Document Solution ID: XK3MG
- PubMed Identifier: 34585790
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 68
- Zeitschrift
- CHEMISTRY-A EUROPEAN JOURNAL
- Schlüsselwörter
- carbon nitrides
- hydrogen
- photocatalysis
- solar energy conversion
- visible light
- Paginierung
- 17188 - 17202
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Titel
- A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption
- Sub types
- Article
- Ausgabe der Zeitschrift
- 27
Data source: Web of Science (Lite)
- Other metadata sources:
-
- Abstract
- <jats:title>Abstract</jats:title><jats:p>The unique optical and photoredox properties of heptazine‐based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430–450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high‐temperature (900 °C) treatment procedure for turning the conventional melamine‐derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de‐ammonification leads to the formation of azo‐groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible‐light (470 nm) for H<jats:sub>2</jats:sub> evolution even without any additional co‐catalyst, but are also responsible for enhanced charge‐trapping and radiative recombination, as shown by spectroscopic studies.</jats:p>
- Autoren
- Dariusz Mitoraj
- Igor Krivtsov
- Chunyu Li
- Ashwene Rajagopal
- Changbin Im
- Christiane Adler
- Kerstin Köble
- Olena Khainakova
- Julian Hniopek
- Christof Neumann
- Andrey Turchanin
- Ivan da Silva
- Michael Schmitt
- Robert Leiter
- Tibor Lehnert
- Jürgen Popp
- Ute Kaiser
- Timo Jacob
- Carsten Streb
- Benjamin Dietzek
- Radim Beranek
- DOI
- 10.1002/chem.202102945
- eISSN
- 1521-3765
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 68
- Zeitschrift
- Chemistry – A European Journal
- Sprache
- en
- Online publication date
- 2021
- Paginierung
- 17188 - 17202
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Herausgeber
- Wiley
- Herausgeber URL
- http://dx.doi.org/10.1002/chem.202102945
- Datum der Datenerfassung
- 2023
- Titel
- A Study in Red: The Overlooked Role of Azo‐Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption
- Ausgabe der Zeitschrift
- 27
Data source: Crossref
- Abstract
- The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430-450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H<sub>2</sub> evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies.
- Addresses
- Institute of Electrochemistry Chemistry, Ulm University, Albert-Einstein-Allee 47, 89081, Ulm, Germany.
- Autoren
- Dariusz Mitoraj
- Igor Krivtsov
- Chunyu Li
- Ashwene Rajagopal
- Changbin Im
- Christiane Adler
- Kerstin Köble
- Olena Khainakova
- Julian Hniopek
- Christof Neumann
- Andrey Turchanin
- Ivan da Silva
- Michael Schmitt
- Robert Leiter
- Tibor Lehnert
- Jürgen Popp
- Ute Kaiser
- Timo Jacob
- Carsten Streb
- Benjamin Dietzek
- Radim Beranek
- DOI
- 10.1002/chem.202102945
- eISSN
- 1521-3765
- Externe Identifier
- PubMed Identifier: 34585790
- PubMed Central ID: PMC9298046
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: INST 275/257-1 FUGG
- Deutsche Forschungsgemeinschaft: BE 5102/5-1
- Ministerio de Ciencia e Innovación: PID2020-113558RB-C41
- Deutsche Forschungsgemeinschaft: TU 149/8-2
- Alexander von Humboldt-Stiftung:
- Deutsche Forschungsgemeinschaft: INST 40/467-1 FUGG
- Deutsche Forschungsgemeinschaft: 364549901
- Open access
- true
- ISSN
- 0947-6539
- Ausgabe der Veröffentlichung
- 68
- Zeitschrift
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Sprache
- eng
- Medium
- Print-Electronic
- Online publication date
- 2021
- Open access status
- Open Access
- Paginierung
- 17188 - 17202
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Publisher licence
- CC BY
- Datum der Datenerfassung
- 2021
- Titel
- A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption.
- Sub types
- research-article
- Journal Article
- Ausgabe der Zeitschrift
- 27
Files
https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/chem.202102945 https://europepmc.org/articles/PMC9298046?pdf=render
Data source: Europe PubMed Central
- Abstract
- The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430-450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H2 evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies.
- Autoren
- Dariusz Mitoraj
- Igor Krivtsov
- Chunyu Li
- Ashwene Rajagopal
- Changbin Im
- Christiane Adler
- Kerstin Köble
- Olena Khainakova
- Julian Hniopek
- Christof Neumann
- Andrey Turchanin
- Ivan da Silva
- Michael Schmitt
- Robert Leiter
- Tibor Lehnert
- Jürgen Popp
- Ute Kaiser
- Timo Jacob
- Carsten Streb
- Benjamin Dietzek
- Radim Beranek
- Autoren-URL
- https://www.ncbi.nlm.nih.gov/pubmed/34585790
- DOI
- 10.1002/chem.202102945
- eISSN
- 1521-3765
- Externe Identifier
- PubMed Central ID: PMC9298046
- Funding acknowledgements
- Deutsche Forschungsgemeinschaft: 364549901
- Deutsche Forschungsgemeinschaft: BE 5102/5-1
- Deutsche Forschungsgemeinschaft: INST 40/467-1 FUGG
- Deutsche Forschungsgemeinschaft: TU 149/8-2
- Deutsche Forschungsgemeinschaft: INST 275/257-1 FUGG
- Ministerio de Ciencia e Innovación: PID2020-113558RB-C41
- Alexander von Humboldt-Stiftung:
- Ausgabe der Veröffentlichung
- 68
- Zeitschrift
- Chemistry
- Schlüsselwörter
- carbon nitrides
- hydrogen
- photocatalysis
- solar energy conversion
- visible light
- Sprache
- eng
- Country
- Germany
- Paginierung
- 17188 - 17202
- Datum der Veröffentlichung
- 2021
- Status
- Published
- Titel
- A Study in Red: The Overlooked Role of Azo-Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption.
- Sub types
- Journal Article
- Ausgabe der Zeitschrift
- 27
Data source: PubMed
- Beziehungen:
- Property of