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Two-dimensional gersiloxenes with tunable bandgap for photocatalytic H2 evolution and CO2 photoreduction to CO.

ABSTRACT: The discovery of graphene and graphene-like two-dimensional materials has brought fresh vitality to the field of photocatalysis. Bandgap engineering has always been an effective way to make semiconductors more suitable for specific applications such as photocatalysis and optoelectronics. Achieving control over the bandgap helps to improve the light absorption capacity of the semiconductor materials, thereby improving the photocatalytic performance. This work reports two-dimensional -H/-OH terminal-substituted siligenes (gersiloxenes) with tunable bandgap. All gersiloxenes are direct-gap semiconductors and have wide range of light absorption and suitable band positions for light driven water reduction into H2, and CO2 reduction to CO under mild conditions. The gersiloxene with the best performance can provide a maximum CO production of 6.91?mmol?g-1?h-1, and a high apparent quantum efficiency (AQE) of 5.95% at 420?nm. This work may open up new insights into the discovery, research and application of new two-dimensional materials in photocatalysis.

SUBMITTER: Zhao F

PROVIDER: S-EPMC7081354 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Two-dimensional gersiloxenes with tunable bandgap for photocatalytic H<sub>2</sub> evolution and CO<sub>2</sub> photoreduction to CO.

Zhao Fulai F Feng Yiyu Y Wang Yu Y Zhang Xin X Liang Xuejing X Li Zhen Z Zhang Fei F Wang Tuo T Gong Jinlong J Feng Wei W

Nature communications 20200319 1

The discovery of graphene and graphene-like two-dimensional materials has brought fresh vitality to the field of photocatalysis. Bandgap engineering has always been an effective way to make semiconductors more suitable for specific applications such as photocatalysis and optoelectronics. Achieving control over the bandgap helps to improve the light absorption capacity of the semiconductor materials, thereby improving the photocatalytic performance. This work reports two-dimensional -H/-OH termin ...[more]

PMID: 32193373

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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.

Dataset Information

Two-dimensional gersiloxenes with tunable bandgap for photocatalytic H2 evolution and CO2 photoreduction to CO.

Publications

Two-dimensional gersiloxenes with tunable bandgap for photocatalytic H<sub>2</sub> evolution and CO<sub>2</sub> photoreduction to CO.

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