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Tuning the Porosity and Photocatalytic Performance of Triazine‐Based Graphdiyne Polymers through Polymorphism
Author(s) -
Schwarz Dana,
Acharjya Amitava,
Ichangi Arun,
Kochergin Yaroslav S.,
Lyu Pengbo,
Opanasenko Maksym V.,
Tarábek Ján,
Vacek Chocholoušová Jana,
Vacek Jaroslav,
Schmidt Johannes,
Čejka Jiří,
Nachtigall Petr,
Thomas Arne,
Bojdys Michael J.
Publication year - 2019
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201802034
Subject(s) - amorphous solid , materials science , polymer , photocatalysis , polymerization , catalysis , chemical engineering , porosity , polymer chemistry , crystallography , chemistry , organic chemistry , composite material , engineering
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, two porous polymorphs of a triazine‐based graphdiyne (TzG) framework are synthesized by a simple, one‐pot homocoupling polymerization reaction using as catalysts Cu I for TzG Cu and Pd II /Cu I for TzG Pd/Cu . The polymers form through irreversible coupling reactions and give rise to a crystalline (TzG Cu ) and an amorphous (TzG Pd/Cu ) polymorph. Notably, the crystalline and amorphous polymorphs are narrow‐gap semiconductors with permanent surface areas of 660 m 2 g −1 and 392 m 2 g −1 , respectively. Hence, both polymers are ideal heterogeneous photocatalysts for water splitting with some of the highest hydrogen evolution rates reported to date (up to 972 μmol h −1 g −1 with and 276 μmol h −1 g −1 without Pt cocatalyst). Crystalline order is found to improve delocalization, whereas the amorphous polymorph requires a cocatalyst for efficient charge transfer. This will need to be considered in future rational design of polymer catalysts and organic electronics.