Shining a Light on <i>s</i>-Triazine-Based Polymers

Butchosa, Cristina; McDonald, Tom O.; Cooper, Andrew I.; Adams, Dave J.; Zwijnenburg, Martijn A.

doi:10.1021/jp411854f

Cited by 52 publications

(44 citation statements)

References 48 publications

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“…In the remainder we will discuss insights into polymer photocatalysts for water splitting from computational modeling, focussing on examples from work from our group . Except where explicitly stated otherwise, all calculations discussed below are based on a combination of density functional theory (DFT) and time‐dependent DFT (TD‐DFT), and use the B3LYP density functional.…”

Section: Insight From Computational Modelingmentioning

confidence: 99%

“…Finally, nearly nothing is known about the underlying reaction mechanism(s). In this article, we will review what one can learn about such questions from computational modeling of polymer photocatalysts, focussing on examples from work from our group [ 24,29,[32][33][34] and our experimental collaborators at the University of Liverpool: the groups of Prof. Andrew Cooper and Prof. Dave Adams. [ 24,29,32 ] We will start, however, with a brief introduction to the physical chemistry of photocatalytic water splitting.…”

Section: Young Talents In Polymer Sciencementioning

confidence: 99%

“…In the remainder we will discuss insights into polymer photocatalysts for water splitting from computational modeling, focussing on examples from work from our group. [ 24,29,[32][33][34] Except where explicitly stated otherwise, all calculations discussed below are based on a combination of density functional theory (DFT) and time-dependent DFT (TD-DFT), and use the B3LYP [35][36][37][38] density functional. The effect of the dielectric environment in which the polymer is embedded, critical for prediction of realistic polymer potentials, is modeled using the COSMO dielectric screening model [ 39 ] and generally a relative dielectric permittivity of 80.1, i.e., water (see Section 1 of the Supporting Information for more details).…”

Section: Insight From Computational Modelingmentioning

confidence: 99%

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Polymer Photocatalysts for Water Splitting: Insights from Computational Modeling

Guiglion

Butchosa

Zwijnenburg

2015

Macro Chemistry & Physics

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Based on insights from computational chemistry calculations, the ability of polymers to act as water splitting photocatalysts for the production of renewable hydrogen from water and sunlight is discussed. Specifically, the important role of exciton dissociation in these materials is highlighted, as well as the possible microscopic origins of the experimentally observed changes in the photocatalytic activity of a polymer with increasing chain length or changing chemical composition. The reason why water oxidation, with polymeric photocatalysts, is difficult, and which polymer properties to target when developing new polymers for water splitting photocatalysis are, finally, also discussed.

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Section: Insight From Computational Modelingmentioning

confidence: 99%

Section: Young Talents In Polymer Sciencementioning

confidence: 99%

Section: Insight From Computational Modelingmentioning

confidence: 99%

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Polymer Photocatalysts for Water Splitting: Insights from Computational Modeling

Guiglion

Butchosa

Zwijnenburg

2015

Macro Chemistry & Physics

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“…Covalent triazine-based frameworks (CTFs) as a typical COFs are composed of triazine units, [19][20][21][22] thus offering them with high chemical and thermal stability. CTFs with the π-stacked aromatic units would be expected to promote exciton separation and charge transport, [ 23,24 ] which is preferred for photocatalysis. So far, they have been explored as potential sorbents [25][26][27][28] and catalytic support.…”

Section: Introductionmentioning

confidence: 99%

Covalent Triazine‐Based Frameworks as Visible Light Photocatalysts for the Splitting of Water

Fang

et al. 2015

Macromol. Rapid Commun.

257

199

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Covalent triazine-based frameworks (CTFs) with a graphene-like layered morphology have been controllably synthesized by the trifluoromethanesulfonic acid-catalyzed nitrile trimerization reactions at room temperature via selecting different monomers. Platinum nanoparticles are well dispersed in CTF-T1, which is ascribed to the synergistic effects of the coordination of triazine moieties and the nanoscale confinement effect of CTFs. CTF-T1 exhibits excellent photocatalytic activity and stability for H2 evolution in the presence of platinum under visible light irradiation (λ ≥ 420 nm). The activity and stability of CTF-T1 are comparable to those of g-C3 N4 . Importantly, as a result of the tailorable electronic and spatial structures of CTFs that can be achieved through the judicial selection of monomers, CTFs not only show great potential as organic semiconductor for photocatalysis but also may provide a molecular-level understanding of the inherent heterogeneous photocatalysis.

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“…In a systematic bottom‐up approach, the evolution of the electronic spectra along the transition from the monomeric chromophore to the polymer can be systematically studied by calculations of absorption spectra for dimers, trimers, etc., as demonstrated, for example, by Butchosa et al. for triazine oligomers or heptazine oligomers . The effect of conjugation of aromatic building blocks on the absorption spectra can thus be elucidated.…”

Section: Hydrogen‐bonded Chromophore‐water Clustersmentioning

confidence: 85%

Solar Energy Harvesting with Carbon Nitrides and N‐Heterocyclic Frameworks: Do We Understand the Mechanism?

2018

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The photocatalytic splitting of water into molecular hydrogen and molecular oxygen with sunlight is the dream reaction for solar energy conversion. For decades, transition metal oxide semiconductors and supramolecular organometallic structures have been extensively explored as photocatalysts for solar water splitting. More recently, polymeric materials consisting of triazine or heptazine building blocks have attracted considerable attention as hydrogen‐evolution photocatalysts. The mechanism of hydrogen evolution with these materials is discussed throughout the current literature in terms of the familiar concepts developed for photoelectrochemical water splitting with semiconductors since the 1970s. We discuss in this Minireview an alternative mechanistic paradigm for photoinduced water splitting with carbon nitrides, which focusses on the specific features of the photochemistry of aromatic N‐heterocycles in aqueous environments. Using ab initio electronic‐structure calculations, it is shown that a water molecule which is hydrogen‐bonded to an N‐heterocycle can be decomposed into hydrogen and hydroxyl radicals by two simple sequential photochemical reactions. This concept is illustrated by the discussion of excited‐state reaction paths and their energy profiles for hydrogen‐bonded complexes of pyridine, triazine and heptazine with a water molecule. It is shown that the excited‐state hydrogen‐transfer and hydrogen‐detachment reactions are essentially barrierless, in sharp contrast to water oxidation in the electronic ground state, where high barriers prevail. We also discuss in some detail the products of possible reactions of the highly reactive photogenerated hydroxyl radicals with the chromophores. We hypothesize that the challenge of efficient solar hydrogen generation with carbon nitride materials is less the decomposition of water as such, but rather the controlled recombination of the photogenerated radicals to the closed‐shell products H2 and H2O2.

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Shining a Light on s-Triazine-Based Polymers

Abstract: ESI-1 TP 3 stacked structuresFig. S1 Calculated spectra of TP3 crystal structure (CS1), a stack of two and three of these molecules (CS2 and CS3 respectively) and a laterally arranged CS2 stacks

Cited by 52 publications

References 48 publications

Polymer Photocatalysts for Water Splitting: Insights from Computational Modeling

Polymer Photocatalysts for Water Splitting: Insights from Computational Modeling

Covalent Triazine‐Based Frameworks as Visible Light Photocatalysts for the Splitting of Water

Solar Energy Harvesting with Carbon Nitrides and N‐Heterocyclic Frameworks: Do We Understand the Mechanism?

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