Tethered sensitizer–catalyst noble-metal-free molecular devices for solar-driven hydrogen generation

Luo, Geng‐Geng; Pan, Zhong-Hua; Lin, Jinqing; Sun, Di

doi:10.1039/c8dt02831a

Cited by 16 publications

(13 citation statements)

References 85 publications

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“…The conversion of solar energy into a storable fuel, such as hydrogen (H 2 ) through sunlight-driven water splitting, is currently the subject of intensive research efforts [1,2]. In that context, photosynthesis has been a great source of inspiration for molecular chemists, leading to the development of a wide variety of H 2 -evolving molecular dyads [3][4][5][6][7][8][9][10][11][12][13], inspired by the Photosystem I-Hydrogenase couple found in some hydrogen producing photosynthetic micro-organisms [14]. Recently, the first functional H 2 -evolving photocathodes integrating such molecular dyads were reported in the literature [2,5,9,11,15], paving the way for solar fuels production in dye-sensitized photoelectrochemical cells.…”

Section: Introductionmentioning

confidence: 99%

Investigating Light-Induced Processes in Covalent Dye-Catalyst Assemblies for Hydrogen Production

et al. 2020

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The light-induced processes occurring in two dye-catalyst assemblies for light-driven hydrogen production were investigated by ultrafast transient absorption spectroscopy. These dyads consist of a push-pull organic dye based on a cyclopenta[1,2-b:5,4-b’]dithiophene (CPDT) bridge, covalently linked to two different H2-evolving cobalt catalysts. Whatever the nature of the latter, photoinduced intramolecular electron transfer from the excited state of the dye to the catalytic center was never observed. Instead, and in sharp contrast to the reference dye, a fast intersystem crossing (ISC) populates a long-lived triplet excited state, which in turn non-radiatively decays to the ground state. This study thus shows how the interplay of different structures in a dye-catalyst assembly can lead to unexpected excited state behavior and might open up new possibilities in the area of organic triplet sensitizers. More importantly, a reductive quenching mechanism with an external electron donor must be considered to drive hydrogen production with these dye-catalyst assemblies.

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Section: Introductionmentioning

confidence: 99%

Investigating Light-Induced Processes in Covalent Dye-Catalyst Assemblies for Hydrogen Production

et al. 2020

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“…A rhodium(II) paddle-wheel unit was employed as the catalytic node because the paddle-wheel motif is highly symmetric ( D 4 h ) and suitable for self-assembly, and several dirhodium complexes are known to catalyze H 2 production . BDP units were selected because BDP derivatives are known to exhibit intense absorption bands in the visible region and can be utilized as the PS for HER . Note that the BDP moieties are also highly effective noncovalent interaction sites because the BF 2 segment of BDP can typically form B–F···H hydrogen-bonding interactions, and the pyrrole moieties can exhibit CH···π interactions …”

Section: Resultsmentioning

confidence: 99%

Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution

et al. 2021

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The direct conversion of solar energy to clean fuels as alternatives to fossil fuels is an important approach for addressing the global energy shortage and environmental problems. Here, we introduce a new dirhodium-complex-based framework assembly as a heterogeneous molecule-based photocatalyst for hydrogen evolution using visible light. Two dirhodium complexes bearing visible-light-harvesting BODIPY (boron dipyrromethene, BDP) moieties were newly designed and synthesized. The obtained complexes were self-assembled to framework structures (supramolecular framework catalysts), which are stabilized intermolecular noncovalent interactions. These frameworks retained excellent visible-light-harvesting properties of BDP moieties. Investigation of the catalytic performance of the supramolecular framework catalysts revealed that the supramolecular framework catalyst with heavy atoms at BDP moieties exhibited excellent performance in the formation of hydrogen with a reaction rate of 275.8 μmol g–1 h–1 under irradiation of visible light, whereas the supramolecular framework catalyst without heavy atoms at BDP moieties was inactive. Moreover, the system has the additional benefits of high durability (up to 96 h), reusability, and facile removal from the reaction mixture. We also disclosed the effect of heavy atoms at BDP moieties on the catalytic activity and proposed a reaction mechanism.

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“…Luo et al also studied a series of BODIPY-sensitized cobaloxime with para -pyridyl and meta -pyridyl substituted BODIPYs as photocatalysts for H 2 production (Figure ). , CoBDP-3-I 2 , containing a meta -pyridyl at the 8-position of BODIPY, shows efficient photocatalytic performance of H 2 production with a TON of 85, as comparable to analogue CoBDP-1-I 2 , i.e., para -pyridyl substituted 2,6-diiodo BODIPY-sensitized cobaloxime, which shows a TON of 82. However, under the same experimental conditions, the noniodinated BODIPY-sensitizer cobaloximes ( CoBDP-1 and CoBDP-3 ) exhibit no photocatalytic activity .…”

Section: Triplet Photosensitizers Showing Strong Absorption Of Visibl...mentioning

confidence: 99%

Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

et al. 2021

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Triplet photosensitizers (PSs) have been studied as photocatalysts in photocatalytic H2 evolution by water splitting and photoredox catalytic synthetic organic reactions, etc. The applications share common features that the photocatalysts (triplet PSs) harvest the photoexcitation energy, then undergo intersystem crossing (ISC), and finally initiate the electron transfer or triplet energy transfer, which are intermolecular processes in most cases. Thus, triplet PSs showing a strong visible-light-harvesting ability and long triplet excited state lifetimes are desired because they can enhance the above intermolecular processes. The conventional transition metal complexes (i.e., Ru(bpy)3X2 or Ir(ppy)3) have been widely used; however, these complexes are not satisfactory due to their weak absorption of visible light and short triplet excited state lifetimes. To a large extent, the photophysical property of these complexes is due to the low-lying metal-to-ligand charge transfer (MLCT) state, the S0 → 1MLCT transition is weakly allowed, and a strong heavy atom effect exists for the 3MLCT state, which results in weak visible light absorption and a short triplet excited state lifetime, respectively. This mini review introduces the recent progress of the development of the transition metal complexes as well as the organic triplet PSs that show a strong visible-light-harvesting ability and long triplet excited state lifetimes. The application of these new triplet PSs in photocatalytic H2 evolution and photoredox catalytic synthetic organic reactions is summarized.

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Tethered sensitizer–catalyst noble-metal-free molecular devices for solar-driven hydrogen generation

Abstract: Recent advances in the all-abundant-element molecular devices for solar-driven H2generationviaintramolecular processes are overviewed including their assembly approaches, and structure–catalytic activity relationships.

Cited by 16 publications

References 85 publications

Investigating Light-Induced Processes in Covalent Dye-Catalyst Assemblies for Hydrogen Production

Investigating Light-Induced Processes in Covalent Dye-Catalyst Assemblies for Hydrogen Production

Dirhodium-Based Supramolecular Framework Catalyst for Visible-Light-Driven Hydrogen Evolution

Triplet Photosensitizers Showing Strong Absorption of Visible Light and Long-Lived Triplet Excited States and Application in Photocatalysis: A Mini Review

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