10.1002/cssc.201802034
https://zenodo.org/records/1471618
oai:zenodo.org:1471618
Schwarz, Dana
Dana
Schwarz
Acharjya, Amitava
Amitava
Acharjya
0000-0002-0998-171X
Ichangi, Arun
Arun
Ichangi
0000-0002-3094-4331
Kochergin, Yaroslav
Yaroslav
Kochergin
0000-0002-9060-6350
Lyu, Pengbo
Pengbo
Lyu
Opanasenko, Maksym V.
Maksym V.
Opanasenko
Tarábek, Jan
Jan
Tarábek
Vacek Chocholoušová, Jana
Jana
Vacek Chocholoušová
Vacek, Jaroslav
Jaroslav
Vacek
Schmidt, Johannes
Johannes
Schmidt
Nachtigall, Petr
Petr
Nachtigall
Thomas, Arne
Arne
Thomas
0000-0002-2130-4930
Bojdys, Michael J.
Michael J.
Bojdys
0000-0002-2592-4168
Humboldt-Universität zu Berlin
Tuning the porosity and photocatalytic performance of triazinebased graphdiyene polymers via polymorphism
Zenodo
2018
graphdiyene
photocatalysis
covalent organic frameworks
conjugated microporous polymers
semiconductors
2018-10-18
https://zenodo.org/communities/eu
Creative Commons Attribution Non Commercial No Derivatives 4.0 International
Crystalline and amorphous organic materials are an
emergent class of heterogeneous photocatalysts for the generation of
hydrogen from water, but a direct correlation between their structures
and the resulting properties has not been achieved so far. To make a
meaningful comparison between structurally different, yet chemically
similar porous polymers, we present two porous polymorphs of a
triazine-based graphdiyene (TzG) framework from a simple, one-pot
reaction using Cu(I) for TzGCu and Pd(II)/Cu(I) for TzGPd/Cu catalyzed
homocoupling polymerization. The polymers form via irreversible
coupling reactions and give rise to a crystalline (TzGCu) and an
amorphous (TzGPd/Cu) polymorph. Notably, the crystalline and
amorphous polymorphs are narrow-gap semiconductors with
permanent surface areas of 660 m2 g-1 and 392 m2 g-1, respectively.
Hence, both polymers are ideal heterogeneous photocatalysts for
water splitting with some of the highest hydrogen evolution rates
reported thus far up to 972 μmol h-1 g-1 with and 276 μmol h-1 g-1
without Pt co-catalyst. We conclude, that crystalline order improves
delocalisation, while the amorphous polymorph requires a co-catalyst
for efficient charge transfer; this will need to be considered in future
rational design of polymer catalysts and organic electronics.
European Commission
10.13039/501100000780
678462
Layered functional materials - beyond 'graphene'