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

• Published in: Molecules (Basel, Switzerland) Switzerland), 2023-03, Vol.28 (7), p.3105
• Main Authors: Chen, Furong, Wiriyarattanakul, Amphawan, Xie, Wanting, Shi, Liyi, Rungrotmongkol, Thanyada, Jia, Rongrong, Maitarad, Phornphimon
• Format: Article
• Language: English
• Subjects: Carbon; Carbon dioxide; catalyst design; Catalysts; Chemical reactions; CO2RR; Density functional theory; Dependent variables; DFT; Electrochemistry; Genetic algorithms; Hydrogen; Mathematical models; metalloporphyrin; Metals; Nitrogen atoms; Porphyrins; QSER; Reduction (metal working); Statistical analysis; Transition metals
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules28073105

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.