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
VL - 126
SP - 283
EP - 290
JO - Polymer
JF - Polymer
SN - 0032-3861
ER -