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- ItemDonor-acceptor covalent organic frameworks for visible light induced free radical polymerization(Cambridge : RSC, 2019) Pachfule, Pradip; Acharjya, Amitava; Roeser, Jérôme; Sivasankaran, Ramesh P.; Ye, Meng-Yang; Brückner, Angelika; Schmidt, Johannes; Thomas, ArneCovalent organic frameworks (COFs) are promising materials for applications in photocatalysis, due to their conjugated, porous and chemically stable architectures. Alternating electron donor-acceptor-type structures are known to enhance charge carrier transport mobility and stability in polymers and are therefore also interesting building units for COFs used as photocatalysts but also as photoinitiator. In this work, two donor-acceptor COFs using electron deficient 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-b]thiophene-2,5-dicarbaldehyde or [2,2′-bithiophene]-5,5′-dicarbaldehyde linkers are presented. The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA). These results pave the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light. © The Royal Society of Chemistry 2019.
- ItemTwo-photon, visible light water splitting at a molecular ruthenium complex(Cambridge : RSC Publ., 2021) Schneidewind, Jacob; Argüello Cordero, Miguel A.; Junge, Henrik; Lochbrunner, Stefan; Beller, MatthiasWater splitting to give molecular oxygen and hydrogen or the corresponding protons and electrons is a fundamental four-electron redox process, which forms the basis of photosynthesis and is a promising approach to convert solar into chemical energy. Artificial water splitting systems have struggled with orchestrating the kinetically complex absorption of four photons as well as the difficult utilization of visible light. Based on a detailed kinetic, spectroscopic and computational study of Milstein's ruthenium complex, we report a new mechanistic paradigm for water splitting, which requires only two photons and offers a new method to extend the range of usable wavelengths far into the visible region. We show that two-photon water splitting is enabled by absorption of the first, shorter wavelength photon, which produces an intermediate capable of absorbing the second, longer wavelength photon (up to 630 nm). The second absorption then causes O–O bond formation and liberation of O2. Theoretical modelling shows that two-photon water splitting can be used to achieve a maximum solar-to-hydrogen efficiency of 18.8%, which could be increased further to 28.6% through photochemical instead of thermal H2 release. It is therefore possible to exceed the maximum efficiency of dual absorber systems while only requiring a single catalyst. Due to the lower kinetic complexity, intrinsic utilization of a wide wavelength range and high-performance potential, we believe that this mechanism will inspire the development of a new class of water splitting systems that go beyond the reaction blueprint of photosynthesis.
- ItemRoom temperature synthesis of an amorphous MoS2 based composite stabilized by N-donor ligands and its light-driven photocatalytic hydrogen production(London : RSC Publishing, 2015) Niefind, Felix; Djamil, John; Bensch, Wolfgang; Srinivasan, Bikshandarkoil R.; Sinev, Ilya; Grünert, Wolfgang; Deng, Mao; Kienle, Lorenz; Lotnyk, Andriy; Mesch, Maria B.; Senker, Jürgen; Dura, Laura; Beweries, TorstenHerein an entirely new and simple room temperature synthesis of an amorphous molybdenum sulfide stabilized by complexing ammonia and hydrazine is reported. The resulting material exhibits an outstanding activity for the photocatalytic hydrogen evolution driven by visible light. It is chemically stable during the reaction conditions of the photocatalysis and shows unusual thermal stability up to 350 °C without crystallization. The new material is obtained by a reaction of solid ammonium tetrathiomolybdate and gaseous hydrazine. In the as-prepared state Mo atoms are surrounded by μ2-briding S2−, NH3 and hydrazine, the latter being coordinated to Mo(IV) in a bridging or side-on mode. Heating at 450 °C or irradiation with an electron beam generates nanosized crystalline MoS2 slabs. The two modes for crystallization are characterized by distinct mechanisms for crystal growth. The stacking of the slabs is low and the material exhibits a pronounced turbostratic disorder. Heat treatment at 900 °C yields more ordered MoS2 but structural disorder is still present. The visible-light driven hydrogen evolution experiments evidence an outstanding performance of the as-prepared sample. The materials were thoroughly characterized by optical spectroscopy, chemical analysis, in situ HRTEM, XRD, 1H and 15N solid-state NMR, XPS, and thermal analysis.