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

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...

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Bibliographic Details
Published in:Chemistry of materials 2015-12, Vol.27 (24), p.8237-8247
Main Authors: Bhunia, Manas K, Melissen, Sigismund, Parida, Manas R, Sarawade, Pradip, Basset, Jean-Marie, Anjum, Dalaver H, Mohammed, Omar F, Sautet, Philippe, Le Bahers, Tangui, Takanabe, Kazuhiro
Format: Article
Language:English
Subjects:
Catalysis
Chemical Sciences
Inorganic chemistry
Material chemistry
Organic chemistry
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Summary: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 consisting 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 negative 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. Because of 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 excited charge carriers for an improved photocatalytic performance. The photocatalytic activity was improved by providing a dendritic tip-on-like shape grown on porous fibrous silica KCC-1 spheres, and highly dispersed Pt nanoparticles (
ISSN:0897-4756
1520-5002
DOI:10.1021/acs.chemmater.5b02974