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Photochemical reduction of CO₂ into CO coupling with triethanolamine decomposition.

ABSTRACT: In this work, the impacts of triethanolamine (TEOA) on the performance of photochemical CO₂ reduction were investigated in a simple homogeneous system. We demonstrates that CO₂ can be converted into CO coupling with the decomposition of triethanolamine in TEOA aqueous solution without other additives under light irradiation. About 7.5 μmol CO product is achieved within 7 h with a maximum apparent quantum yield (AQY) of 0.086% at 254 nm. The isotope labelling experiment confirms that CO product originates from the reduction of CO₂ rather than the decomposition of TEOA. In addition, the photochemical system exhibits excellent stability, no obvious inactivation is observed during long-term photochemical CO₂ reduction reaction. This work provides a deep understanding of the effects of TEOA on the performance of photocatalytic CO₂ reduction. Upon utilizing TEOA as a sacrificial electron donor in photocatalytic system, the contribution of TEOA must be considered once evaluating the catalytic activity of catalysts.

SUBMITTER: Li Z

PROVIDER: S-EPMC10614036 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Photochemical reduction of CO2 into CO coupling with triethanolamine decomposition.

Li Zhen Z Yang Caili C Su Yingshi Y Cheng Yonghui Y Cui Yanjia Y Liu Suyao S Fang Yiwen Y

RSC advances 20231030 45

In this work, the impacts of triethanolamine (TEOA) on the performance of photochemical CO2 reduction were investigated in a simple homogeneous system. We demonstrates that CO2 can be converted into CO coupling with the decomposition of triethanolamine in TEOA aqueous solution without other additives under light irradiation. About 7.5 μmol CO product is achieved within 7 h with a maximum apparent quantum yield (AQY) of 0.086% at 254 nm. The isotope labelling experiment conf ...[more]

PMID: 37908646

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Project description:Photochemical CO2 reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO-) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO-) in the photochemical CO2 reduction: the ratio of CO/HCOO- decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO- is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO-. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO- in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO- formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)-Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work.

Project description:To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to molecular CO2 reduction catalysis. For [FeTPP(CO2-κC)]2- (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO2 binding, -N(CH3)3 + (TMA) and -OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The coulombic interaction between the positively charged TMA group and activated CO2 is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO2 via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible "pockets" in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the p-terphenyl radical anion to CO2, we demonstrate that the double terminal substitution of p-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.

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Photochemical reduction of CO₂ into CO coupling with triethanolamine decomposition.

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Photochemical reduction of CO<sub>2</sub> into CO coupling with triethanolamine decomposition.

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