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Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO₂ photoreduction.

ABSTRACT: Sunlight plays a critical role in the development of emerging sustainable energy conversion and storage technologies. Light-induced CO₂ reduction by artificial photosynthesis is one of the cornerstones to produce renewable fuels and environmentally friendly chemicals. Interface interactions between plasmonic metal nanoparticles and semiconductors exhibit improved photoactivities under a wide range of the solar spectrum. However, the photo-induced charge transfer processes and their influence on photocatalysis with these materials are still under debate, mainly due to the complexity of the involved routes occurring at different timescales. Here, we use a combination of advanced in situ and time-resolved spectroscopies covering different timescales, combined with theoretical calculations, to unravel the overall mechanism of photocatalytic CO₂ reduction by Ag/TiO₂ catalysts. Our findings provide evidence of the key factors determining the enhancement of photoactivity under ultraviolet and visible irradiation, which have important implications for the design of solar energy conversion materials.

SUBMITTER: Collado L

PROVIDER: S-EPMC6255847 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO<sub>2</sub> photoreduction.

Collado Laura L Reynal Anna A Fresno Fernando F Barawi Mariam M Escudero Carlos C Perez-Dieste Virginia V Coronado Juan M JM Serrano David P DP Durrant James R JR de la Peña O'Shea Víctor A VA

Nature communications 20181126 1

Sunlight plays a critical role in the development of emerging sustainable energy conversion and storage technologies. Light-induced CO<sub>2</sub> reduction by artificial photosynthesis is one of the cornerstones to produce renewable fuels and environmentally friendly chemicals. Interface interactions between plasmonic metal nanoparticles and semiconductors exhibit improved photoactivities under a wide range of the solar spectrum. However, the photo-induced charge transfer processes and their in ...[more]

PMID: 30478316

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Project description:We report a study of the photocatalytic reduction of CO2 to CO by zinc porphyrins covalently linked to [ReI(2,2'-bipyridine)(CO)3L]+/0 moieties with visible light of wavelength >520 nm. Dyad 1 contains an amide C6H4NHC(O) link from porphyrin to bipyridine (Bpy), Dyad 2 contains an additional methoxybenzamide within the bridge C6H4NHC(O)C6H3(OMe)NHC(O), while Dyad 3 has a saturated bridge C6H4NHC(O)CH2; each dyad is studied with either L = Br or 3-picoline. The syntheses, spectroscopic characterisation and cyclic voltammetry of Dyad 3 Br and [Dyad 3 pic]OTf are described. The photocatalytic performance of [Dyad 3 pic]OTf in DMF/triethanolamine (5?:?1) is approximately an order of magnitude better than [Dyad 1 pic]PF6 or [Dyad 2 pic]OTf in turnover frequency and turnover number, reaching a turnover number of 360. The performance of the dyads with Re-Br units is very similar to that of the dyads with [Re-pic]+ units in spite of the adverse free energy of electron transfer. The dyads undergo reactions during photocatalysis: hydrogenation of the porphyrin to form chlorin and isobacteriochlorin units is detected by visible absorption spectroscopy, while IR spectroscopy reveals replacement of the axial ligand by a triethanolaminato group and insertion of CO2 into the latter to form a carbonate. Time-resolved IR spectra of [Dyad 2 pic]OTf and [Dyad 3 pic]OTf (560 nm excitation in CH2Cl2) demonstrated electron transfer from porphyrin to Re(Bpy) units resulting in a shift of ?(CO) bands to low wavenumbers. The rise time of the charge-separated species for [Dyad 3 pic]OTf is longest at 8 (±1) ps and its lifetime is also the longest at 320 (±15) ps. The TRIR spectra of Dyad 1 Br and Dyad 2 Br are quite different showing a mixture of 3MLCT, IL and charge-separated excited states. In the case of Dyad 3 Br, the charge-separated state is absent altogether. The TRIR spectra emphasize the very different excited states of the bromide complexes and the picoline complexes. Thus, the similarity of the photocatalytic data for bromide and picoline dyads suggests that they share common intermediates. Most likely, these involve hydrogenation of the porphyrin and substitution of the axial ligand at rhenium.

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Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO₂ photoreduction.

Publications

Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO<sub>2</sub> photoreduction.

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Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO2 photoreduction.

Publications

Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO<sub>2</sub> photoreduction.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

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Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO₂ photoreduction.