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Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO₂ reduction.

ABSTRACT: We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl-bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO₂ reduction in conjunction with various mononuclear catalysts, such as Re(i), Ru(ii) and Mn(i) metal complexes, employing a relatively weak sacrificial electron donor, triethanolamine. Each system showed good product selectivity (CO or HCOOH) and an excellent quantum yield of product formation Φ_CO = 0.60 to 0.74 using fac-[Re^I(bpy)(CO)₃(CH₃CN)]⁺, Φ_HCOOH = 0.58 using trans(Cl)-Ru^II(dtbb)(CO)₂Cl₂ and Φ_HCOOH = 0.48 using a fac-[Mn^I(dtbb)(CO)₃(CH₃CN)]⁺ catalyst. The high photocatalytic efficiencies for CO₂ reduction are attributed to efficient reductive quenching of the Re-ring by triethanolamine and fast electron transfer from the generated one-electron-reduced species of the ring to the catalyst.

SUBMITTER: Rohacova J

PROVIDER: S-EPMC5355825 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature

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Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO<sub>2</sub> reduction.

Rohacova Jana J Ishitani Osamu O

Chemical science 20160705 11

We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl-bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO<sub>2</sub> reduction in conjunction wi ...[more]

PMID: 28451117

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Project description:Photocatalytic CO2 reduction to valuable hydrocarbon solar fuel is of great significance but still challenging. Strong CO2 enrichment ability and easily adjustable structures make metal-organic frameworks (MOFs) potential photocatalysts for CO2 conversion. Even though pure MOFs have the potential for photoreduction of CO2, the efficiency is still quite low due to rapid photogenerated electron-hole recombination and other drawbacks. In this work, graphene quantum dots (GQDs) were in situ encapsulated into highly stable MOFs via a solvothermal method for this challenging task. The GQDs@PCN-222 with encapsulated GQDs showed similar Powder X-ray Diffraction (PXRD) patterns to PCN-222, indicating the retained structure. The porous structure was also retained with a Brunauer-Emmett-Teller (BET) surface area of 2066 m2/g. After incorporation of GQDs, the shape of GQDs@PCN-222 particles remained, as revealed by the scanning electron microscope (SEM). As most of the GQDs were covered by thick PCN-222, it was hard to observe those GQDs using a transmission electron microscope (TEM) and a high-resolution transmission electron microscope (HRTEM) directly, the treatment of digested GQDs@PCN-222 particles by immersion in a 1 mM aqueous KOH solution can make the incorporated GQDs visible in TEM and HRTEM. The linker, deep purple porphyrins, make MOFs a highly visible light harvester up to 800 nm. The introduction of GQDs inside PCN-222 can effectively promote the spatial separation of the photogenerated electron-hole pairs during the photocatalytic process, which was proved by the transient photocurrent plot and photoluminescence emission spectra. Compared with pure PCN-222, the obtained GQDs@PCN-222 displayed dramatically enhanced CO production derived from CO2 photoreduction with 147.8 μmol/g/h in a 10 h period under visible light irradiation with triethanolamine (TEOA) as a sacrificial agent. This study demonstrated that the combination of GQDs and high light absorption MOFs provides a new platform for photocatalytic CO2 reduction.

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Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO₂ reduction.

Publications

Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO<sub>2</sub> reduction.

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Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction.

Publications

Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO<sub>2</sub> reduction.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

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Rhenium(i) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO₂ reduction.