Tuning the Porosity and Photocatalytic Performance of Triazine-Based Graphdiyne Polymers through Polymorphism
| Autor: | Amitava Acharjya, Michael J. Bojdys, Dana Schwarz, Pengbo Lyu, Jana Vacek Chocholoušová, Arun Ichangi, Ján Tarábek, Arne Thomas, Jaroslav Vacek, Jiří Čejka, Johannes Schmidt, Yaroslav S. Kochergin, Maksym Opanasenko, Petr Nachtigall |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Organic electronics
chemistry.chemical_classification Materials science General Chemical Engineering 02 engineering and technology Polymer 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences 0104 chemical sciences Conjugated microporous polymer Catalysis Amorphous solid General Energy Polymerization Chemical engineering Polymorphism (materials science) chemistry Environmental Chemistry Water splitting General Materials Science 0210 nano-technology |
| Zdroj: | ChemSusChem |
| ISSN: | 1864-564X |
| Popis: | 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 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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text