Tuning the Porosity and Photocatalytic Performance of Triazine-Based Graphdiyne Polymers through Polymorphism

0501539 - ÚOCHB 2020 RIV DE eng J - Journal Article
Schwarz, D. - Acharjya, A. - Ichangi, Arun - Kochergin, Y. S. - Lyu, P. - Opanasenko, Maksym - Tarábek, Ján - Vacek Chocholoušová, Jana - Vacek, Jaroslav - Schmidt, J. - Čejka, Jiří - Nachtigall, P. - Thomas, A. - Bojdys, Michael J.
Tuning the Porosity and Photocatalytic Performance of Triazine-Based Graphdiyne Polymers through Polymorphism.
ChemSusChem. Roč. 12, č. 1 (2019), s. 194-199. ISSN 1864-5631. E-ISSN 1864-564X
Institutional support: RVO:61388963 ; RVO:61388955
Keywords : carbon * covalent organic frameworks * photocatalysis * porous polymers * semiconductors
OECD category: Organic chemistry; Physical chemistry (UFCH-W)
Impact factor: 7.962, year: 2019
Method of publishing: Limited access
https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cssc.201802034

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 mu mol h(-1) g(-1) with and 276 mu mol 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.
Permanent Link: http://hdl.handle.net/11104/0296279