Quantitative Structure-Electrochemistry Relationship (QSER) Studies on Metal-Amino-Porphyrins for the Rational Design of CO2 Reduction Catalysts

Furong Chen; Amphawan Wiriyarattanakul; Wanting Xie; Liyi Shi; Thanyada Rungrotmongkol; Rongrong Jia; Phornphimon Maitarad

doi:10.3390/molecules28073105

Quantitative Structure-Electrochemistry Relationship (QSER) Studies on Metal-Amino-Porphyrins for the Rational Design of CO₂ Reduction Catalysts

Molecules. 2023 Mar 30;28(7):3105. doi: 10.3390/molecules28073105.

Authors

Furong Chen¹, Amphawan Wiriyarattanakul², Wanting Xie¹, Liyi Shi^{1

3}, Thanyada Rungrotmongkol^{4

5}, Rongrong Jia⁶, Phornphimon Maitarad¹

Affiliations

¹ Research Center of Nano Science and Technology, Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China.
² Program in Chemistry, Faculty of Science and Technology, Uttaradit Rajabhat University, Uttaradit 53000, Thailand.
³ Emerging Industries Institute Shanghai University, Jiaxing 314006, China.
⁴ Center of Excellence in Biocatalyst and Sustainable Biotechnology, Department of Biochemistry, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand.
⁵ Program in Bioinformatics and Computational Biology, Graduate School, Chulalongkorn University, Bangkok 10330, Thailand.
⁶ Department of Physics, Materials Genome Institute, Shanghai University, Shanghai 200444, China.

Abstract

The quantitative structure-electrochemistry relationship (QSER) method was applied to a series of transition-metal-coordinated porphyrins to relate their structural properties to their electrochemical CO₂ reduction activity. Since the reactions mainly occur within the core of the metalloporphyrin catalysts, the cluster model was used to calculate their structural and electronic properties using density functional theory with the M06L exchange-correlation functional. Three dependent variables were employed in this work: the Gibbs free energies of H*, C*OOH, and O*CHO. QSER, with the genetic algorithm combined with multiple linear regression (GA-MLR), was used to manipulate the mathematical models of all three Gibbs free energies. The obtained statistical values resulted in a good predictive ability (R² value) greater than 0.945. Based on our QSER models, both the electronic properties (charges of the metal and porphyrin) and the structural properties (bond lengths between the metal center and the nitrogen atoms of the porphyrin) play a significant role in the three Gibbs free energies. This finding was further applied to estimate the CO₂ reduction activities of the metal-monoamino-porphyrins, which will prove beneficial in further experimental developments.

Keywords: CO2RR; DFT; QSER; catalyst design; metalloporphyrin.

Abstract

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