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The economy’s continued demand for high-carbon fuels has led to an increase in carbon dioxide (CO2) in the atmosphere. Even if efforts are made to reduce carbon dioxide emissions, they are not enough to reverse the harmful effects of the gas already in the atmosphere.
So scientists have developed creative ways to use the carbon dioxide already in the atmosphere by converting it into useful molecules such as formic acid (HCOOH) and methanol. Photocatalytic photoreduction of carbon dioxide using visible light is a common method for such transformations.
A team of scientists from the Tokyo Institute of Technology, led by Professor Kazuhiko Maeda, has made major progress and documented it in the international publication “Angewandte Chemie” dated May 8, 2023.
They created a tin-based metal-organic framework (MOF) that enables selective photoreduction of carbon dioxide. The researchers create a new tin (Sn)-based MOF with the chemical formula [SnII2(H3ttc)2.MeOH]n (H3ttc: trithiocyanuric acid and MeOH: methanol).
Most highly efficient visible light-based CO2 photocatalysts use rare precious metals as their main components. Moreover, the integration of light absorption and catalytic functions into a single molecular unit composed of a large number of metals remains a long-standing challenge. Thus, Sn is an ideal candidate because it can solve both problems.
MOFs are the best materials for metals and organic materials, and MOFs are being studied as a greener alternative to traditional rare earth photocatalysts.
Sn is a potential choice for MOF-based photocatalysts because it can act as a catalyst and scavenger during the photocatalytic process. Although lead, iron, and zirconium-based MOFs have been extensively studied, little is known about tin-based MOFs.
H3ttc, MeOH and tin chloride were used as starting ingredients to prepare the tin-based MOF KGF-10, and the researchers decided to use 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole. serves as an electron donor and source of hydrogen.
The resulting KGF-10 is then subjected to various analytical processes. They found that the material has a bandgap of 2.5 eV, absorbs visible light wavelengths, and has a moderate carbon dioxide adsorption capacity.
Once scientists understood the physical and chemical properties of this new material, they used it to catalyze the reduction of carbon dioxide in the presence of visible light. They found that KGF-10 can efficiently and selectively convert CO2 to formate (HCOO–) with up to 99% efficiency without the need for additional photosensitizers or catalysts.
It also has a record high apparent quantum yield (the ratio of the number of electrons involved in the reaction to the total number of incident photons) of 9.8% at a wavelength of 400 nm. Moreover, structural analysis carried out throughout the reaction showed that KGF-10 underwent structural modifications that promoted photocatalytic reduction.
This study presents for the first time a highly efficient, single-component, precious metal-free tin-based photocatalyst to accelerate the conversion of carbon dioxide to formate. The remarkable properties of KGF-10 discovered by the team open new possibilities for its use as a photocatalyst in processes such as reducing CO2 emissions using solar energy.
Professor Maeda concluded: “Our results indicate that MOFs can serve as a platform for using non-toxic, low-cost, and earth-rich metals to create superior photocatalytic functions that are typically unattainable using molecular metal complexes.”
Kamakura Y et al (2023) Tin(II)-based metal-organic frameworks enable efficient and selective reduction of carbon dioxide to formation under visible light. Applied Chemistry, International Edition. doi:10.1002/ani.202305923
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