Dana Schwarz1, Amitava Acharjya2, Arun Ichangi1,3, Yaroslav S. Kochergin1, Pengbo Lyu4, Maksym Opanasenko4,5, Ján Tarábek3, Jana Vacek Chocholoušová3, Jaroslav Vacek3, Johannes Schmidt2, Jiřı́ Čejka4,5, Petr Nachtigall4, Arne Thomas2, Michael J. Bojdys1,3
1Faculty of Science, Department of Organic Chemistry, Charles University, Hlavova 8, 128 43 Prague 2, Czech Republic
2Institute of Chemistry Technische Universität Berlin Hardenbergstraße 40 10623 Berlin Germany
3Institute of Organic Chemistry and Biochemistry of the CAS Flemingovo nám. 2 166 10 Prague 6 Czech Republic
4Faculty of Science, Department of Physical and Macromolecular Chemistry, Charles University, Hlavova 8, 128 43 Prague 2, Czech Republic
5J. Heyrovský Institute of Physical Chemistry of the CAS, v.v.i. Dolejškova 2155/3 182 23 Prague 8 Czech Republic
Tóm tắt
AbstractCrystalline 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 CuI for TzGCu and PdII/CuI for TzGPd/Cu. The polymers form through 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 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.
