Structure-property relationships for covalent triazine-based frameworks: the effect of spacer length on photocatalytic hydrogen evolution from water

Christian B. Meier; Reiner Sebastian Sprick; Adriano Monti; Pierre Guiglion; Jet Sing M. Lee; Martijn A. Zwijnenburg; Andrew I. Cooper

doi:10.1016/j.polymer.2017.04.017

Structure-property relationships for covalent triazine-based frameworks: the effect of spacer length on photocatalytic hydrogen evolution from water

Christian B. Meier, Reiner Sebastian Sprick, Adriano Monti, Pierre Guiglion, Jet Sing M. Lee, Martijn A. Zwijnenburg, Andrew I. Cooper^*

^*Corresponding author for this work

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

148 Citations (Scopus)

33 Downloads (Pure)

Abstract

Covalent triazine-based frameworks (CTFs) are a subclass of conjugated microporous polymers (CMPs) that can be used as organic photocatalysts for photocatalytic hydrogen evolution from water. Seven materials with varied spacer units from phenylene to quarterphenylene were synthesized, either by trifluoromethanesulfonic acid (TfOH) catalysis from nitriles or by Suzuki-Miyaura polycondensation. The photocatalytic performance under visible light of all materials was systematically studied in the presence of a hole-scavenger, showing that both synthesis routes produce CTFs with similar hydrogen evolution rates (HER), but different optical properties. The highest hydrogen evolution rate in the cyclotrimerized series was found for CTF-2 with an apparent quantum yield of 1.6% at 420 nm in a mixture of water and triethanolamine with a platinum co-catalyst. Based on (TD-)DFT calculations, the highest performance was expected for CTF-1 and this discrepancy is explained by a trade-off between increased light absorption and decreased thermodynamic driving force.

Original language	English
Pages (from-to)	283-290
Number of pages	8
Journal	Polymer
Volume	126
DOIs	https://doi.org/10.1016/j.polymer.2017.04.017
Publication status	Published - 22 Sept 2017

Funding

We thank the Engineering and Physical Sciences Research Council for financial support under Grant EP/N004884/1 . M.A.Z. furthermore acknowledge EPSRC for a Career Acceleration Fellowship (Grant EP/I004424/1 ). We acknowledge computational time on the EPSRC National Service for Computational Chemistry Software. C.B.M. thanks Rob Clowes for help with sorption measurements.

Keywords

covalent triazine-based framework (CTF)
hydrogen evolution from water
photocatalysis

Access to Document

10.1016/j.polymer.2017.04.017

Meier-etal-P2017-Structure-property-relationships-covalent-triazine-based-frameworks-effect-spacer-length-photocatalytic-hydrogenFinal published version, 884 KBLicence: CC BY 4.0

Cite this

@article{e3a33b1c6110425fb50de26c9156c1d7,

title = "Structure-property relationships for covalent triazine-based frameworks: the effect of spacer length on photocatalytic hydrogen evolution from water",

abstract = "Covalent triazine-based frameworks (CTFs) are a subclass of conjugated microporous polymers (CMPs) that can be used as organic photocatalysts for photocatalytic hydrogen evolution from water. Seven materials with varied spacer units from phenylene to quarterphenylene were synthesized, either by trifluoromethanesulfonic acid (TfOH) catalysis from nitriles or by Suzuki-Miyaura polycondensation. The photocatalytic performance under visible light of all materials was systematically studied in the presence of a hole-scavenger, showing that both synthesis routes produce CTFs with similar hydrogen evolution rates (HER), but different optical properties. The highest hydrogen evolution rate in the cyclotrimerized series was found for CTF-2 with an apparent quantum yield of 1.6% at 420 nm in a mixture of water and triethanolamine with a platinum co-catalyst. Based on (TD-)DFT calculations, the highest performance was expected for CTF-1 and this discrepancy is explained by a trade-off between increased light absorption and decreased thermodynamic driving force.",

keywords = "covalent triazine-based framework (CTF), hydrogen evolution from water, photocatalysis",

author = "Meier, {Christian B.} and Sprick, {Reiner Sebastian} and Adriano Monti and Pierre Guiglion and Lee, {Jet Sing M.} and Zwijnenburg, {Martijn A.} and Cooper, {Andrew I.}",

year = "2017",

month = sep,

day = "22",

doi = "10.1016/j.polymer.2017.04.017",

language = "English",

volume = "126",

pages = "283--290",

journal = "Polymer",

issn = "0032-3861",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Structure-property relationships for covalent triazine-based frameworks

T2 - the effect of spacer length on photocatalytic hydrogen evolution from water

AU - Meier, Christian B.

AU - Sprick, Reiner Sebastian

AU - Monti, Adriano

AU - Guiglion, Pierre

AU - Lee, Jet Sing M.

AU - Zwijnenburg, Martijn A.

AU - Cooper, Andrew I.

PY - 2017/9/22

Y1 - 2017/9/22

N2 - Covalent triazine-based frameworks (CTFs) are a subclass of conjugated microporous polymers (CMPs) that can be used as organic photocatalysts for photocatalytic hydrogen evolution from water. Seven materials with varied spacer units from phenylene to quarterphenylene were synthesized, either by trifluoromethanesulfonic acid (TfOH) catalysis from nitriles or by Suzuki-Miyaura polycondensation. The photocatalytic performance under visible light of all materials was systematically studied in the presence of a hole-scavenger, showing that both synthesis routes produce CTFs with similar hydrogen evolution rates (HER), but different optical properties. The highest hydrogen evolution rate in the cyclotrimerized series was found for CTF-2 with an apparent quantum yield of 1.6% at 420 nm in a mixture of water and triethanolamine with a platinum co-catalyst. Based on (TD-)DFT calculations, the highest performance was expected for CTF-1 and this discrepancy is explained by a trade-off between increased light absorption and decreased thermodynamic driving force.

AB - Covalent triazine-based frameworks (CTFs) are a subclass of conjugated microporous polymers (CMPs) that can be used as organic photocatalysts for photocatalytic hydrogen evolution from water. Seven materials with varied spacer units from phenylene to quarterphenylene were synthesized, either by trifluoromethanesulfonic acid (TfOH) catalysis from nitriles or by Suzuki-Miyaura polycondensation. The photocatalytic performance under visible light of all materials was systematically studied in the presence of a hole-scavenger, showing that both synthesis routes produce CTFs with similar hydrogen evolution rates (HER), but different optical properties. The highest hydrogen evolution rate in the cyclotrimerized series was found for CTF-2 with an apparent quantum yield of 1.6% at 420 nm in a mixture of water and triethanolamine with a platinum co-catalyst. Based on (TD-)DFT calculations, the highest performance was expected for CTF-1 and this discrepancy is explained by a trade-off between increased light absorption and decreased thermodynamic driving force.

KW - covalent triazine-based framework (CTF)

KW - hydrogen evolution from water

KW - photocatalysis

UR - http://www.scopus.com/inward/record.url?scp=85018988738&partnerID=8YFLogxK

U2 - 10.1016/j.polymer.2017.04.017

DO - 10.1016/j.polymer.2017.04.017

M3 - Article

AN - SCOPUS:85018988738

SN - 0032-3861

VL - 126

SP - 283

EP - 290

JO - Polymer

JF - Polymer

ER -

Structure-property relationships for covalent triazine-based frameworks: the effect of spacer length on photocatalytic hydrogen evolution from water

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this