Dendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activity

Handle URI:
http://hdl.handle.net/10754/583405
Title:
Dendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activity
Authors:
Bhunia, Manas Kumar ( 0000-0001-6884-8217 ) ; Melissen, Sigismund; Parida, Manas R.; Sarawade, Pradip; Basset, Jean-Marie ( 0000-0003-3166-8882 ) ; Anjum, Dalaver H.; Mohammed, Omar F. ( 0000-0001-8500-1130 ) ; Sautet, Philippe; Le Bahers, Tangui; Takanabe, Kazuhiro ( 0000-0001-5374-9451 )
Abstract:
Developing stable, ubiquitous and efficient water-splitting photocatalyst material that has extensive absorption in the visible-light range is desired for a sustainable solar energy-conversion device. We herein report a triazine-based carbon nitride (CN) material with different C/N ratios achieved by varying the monomer composition ratio between melamine (Mel) and 2,4,6-triaminopyrimidine (TAP). The CN material with a different C/N ratio was obtained through a two-step synthesis protocol: starting with the solution state dispersion of the monomers via hydrogen-bonding supramolecular aggregate, followed by a salt-melt high temperature polycondensation. This protocol ensures the production of a highly crystalline polytriazine imide (PTI) structure con-sisting of a copolymerized Mel-TAP network. The observed bandgap narrowing with an increasing TAP/Mel ratio is well simulated by density functional theory (DFT) calculations, revealing a positive shift in the valence band upon substitution of N with CH in the aromatic rings. Increasing the TAP amount could not maintain the crystalline PTI structure, consistent with DFT calculation showing the repulsion associated with additional C-H introduced in the aromatic rings. Due to the high exciton binding energy calculated by DFT for the obtained CN, the cocatalyst must be close to any portion of the material to assist the separation of excit-ed charge carriers for an improved photocatalytic performance. The photocatalytic activity was improved by providing a dendritic tip-on-like shape grown on a porous fibrous silica KCC-1 spheres, and highly dispersed Pt nanoparticles (<5 nm) were photodepos-ited to introduce heterojunction. As a result, the Pt/CN/KCC-1 photocatalyst exhibited an apparent quantum efficiency (AQE) as high as 22.1 ± 3% at 400 nm and the silica was also beneficial for improving photocatalytic stability. The results obtained by time-resolved transient absorption spectroscopy measurements were consistent with the improved photocatalytic activity with the slow-est carrier recombination for the optimized CN photocatalyst.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); Solar and Photovoltaic Engineering Research Center (SPERC); Imaging and Characterization Core Lab
Citation:
Dendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activity 2015 Chemistry of Materials
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
23-Nov-2015
DOI:
10.1021/acs.chemmater.5b02974
Type:
Article
ISSN:
0897-4756; 1520-5002
Additional Links:
http://pubs.acs.org/doi/10.1021/acs.chemmater.5b02974
Appears in Collections:
Articles; Advanced Nanofabrication, Imaging and Characterization Core Lab; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBhunia, Manas Kumaren
dc.contributor.authorMelissen, Sigismunden
dc.contributor.authorParida, Manas R.en
dc.contributor.authorSarawade, Pradipen
dc.contributor.authorBasset, Jean-Marieen
dc.contributor.authorAnjum, Dalaver H.en
dc.contributor.authorMohammed, Omar F.en
dc.contributor.authorSautet, Philippeen
dc.contributor.authorLe Bahers, Tanguien
dc.contributor.authorTakanabe, Kazuhiroen
dc.date.accessioned2015-12-08T13:36:50Zen
dc.date.available2015-12-08T13:36:50Zen
dc.date.issued2015-11-23en
dc.identifier.citationDendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activity 2015 Chemistry of Materialsen
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.5b02974en
dc.identifier.urihttp://hdl.handle.net/10754/583405en
dc.description.abstractDeveloping stable, ubiquitous and efficient water-splitting photocatalyst material that has extensive absorption in the visible-light range is desired for a sustainable solar energy-conversion device. We herein report a triazine-based carbon nitride (CN) material with different C/N ratios achieved by varying the monomer composition ratio between melamine (Mel) and 2,4,6-triaminopyrimidine (TAP). The CN material with a different C/N ratio was obtained through a two-step synthesis protocol: starting with the solution state dispersion of the monomers via hydrogen-bonding supramolecular aggregate, followed by a salt-melt high temperature polycondensation. This protocol ensures the production of a highly crystalline polytriazine imide (PTI) structure con-sisting of a copolymerized Mel-TAP network. The observed bandgap narrowing with an increasing TAP/Mel ratio is well simulated by density functional theory (DFT) calculations, revealing a positive shift in the valence band upon substitution of N with CH in the aromatic rings. Increasing the TAP amount could not maintain the crystalline PTI structure, consistent with DFT calculation showing the repulsion associated with additional C-H introduced in the aromatic rings. Due to the high exciton binding energy calculated by DFT for the obtained CN, the cocatalyst must be close to any portion of the material to assist the separation of excit-ed charge carriers for an improved photocatalytic performance. The photocatalytic activity was improved by providing a dendritic tip-on-like shape grown on a porous fibrous silica KCC-1 spheres, and highly dispersed Pt nanoparticles (<5 nm) were photodepos-ited to introduce heterojunction. As a result, the Pt/CN/KCC-1 photocatalyst exhibited an apparent quantum efficiency (AQE) as high as 22.1 ± 3% at 400 nm and the silica was also beneficial for improving photocatalytic stability. The results obtained by time-resolved transient absorption spectroscopy measurements were consistent with the improved photocatalytic activity with the slow-est carrier recombination for the optimized CN photocatalyst.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/acs.chemmater.5b02974en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/acs.chemmater.5b02974.en
dc.titleDendritic Tip-on Polytriazine-Based Carbon Nitride Photocatalyst with High Hydrogen Evolution Activityen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.contributor.departmentImaging and Characterization Core Laben
dc.identifier.journalChemistry of Materialsen
dc.eprint.versionPost-printen
dc.contributor.institutionUniversité de Lyon, Université Claude Bernard Lyon 1, Centre National de Recherche Scientifique, Ecole Normale Supérieure Lyon, 46 allée d'Italie, 69007 Lyon Cedex 07, Franceen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorBhunia, Manas Kumaren
kaust.authorParida, Manas R.en
kaust.authorSarawade, Pradipen
kaust.authorBasset, Jean-Marieen
kaust.authorAnjum, Dalaver H.en
kaust.authorMohammed, Omar F.en
kaust.authorTakanabe, Kazuhiroen
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