Recent advances in the rational designing of metalloporphyrinoid-based CO2 reduction catalysts: From molecular structural tuning to the application in catalysis

Abstract

Electro and photochemical CO2 reduction (CO2R) has emerged as a contemporary research field for tackling the fossil fuel problems and construction of a modern chemical industry. For efficient CO2R, a catalyst is needed, and Earth-abundant Fe, Co, and Ni-based metalloporphyrinoids have appeared as promising molecular catalysts for CO2R. Several metal complexes of porphyrins, phthalocyanines, corroles, and chlorins-type porphyrinoids have been designed and tested for this purpose. The unique advantages in the judicious tuning of the porphyrinoid structures and their susceptibility towards different functionalization reactions allow an impressive scope to explore and establish a direct structure-activity relationship of metalloporphyrinoids towards CO2R. There have been rapid advances in this field in the last few years. For the homogeneous CO2R, the electronic and steric aspects of the porphyrinoids are fine-controlled by installing favorable functional groups at the periphery of the porphyrinoids. On the other hand, in heterogenous CO2R, the design principle is guided by integrating metalloporphyrinoids in composite material after mixing with carbon supports, semiconductors, or adopting reticular chemistry. All the advancements further result in the testing of excellent metalloporphyrinoids in industrially feasible CO2 electrolyzers or photoelectrochemical devices. This review focuses on the recent advances in designing principles of metalloporphyrnoids catalysts in homogeneous, heterogeneous, and CO2R reactors.

CO2 Reduction by an Iron(I) Porphyrinate System: Effect of Hydrogen Bonding on the Second Coordination Sphere

“…Because CO 2 reduction is a challenging reaction, often transition-metal catalysts are used for this process. − In recent years, however, a number of catalysts with first-row transition-metal elements such as iron or manganese have been identified. − Particularly promising CO 2 reduction catalysts contain an iron­(I) porphyrinate group. , Thus, Chang et al took an iron­(I) tetraphenylporphyrin (TPP) complex and inserted substituents on the ortho and para positions of one of the phenyl groups (Scheme ). These porphyrin derivatives with amide groups in the second coordination sphere were shown to give an enhanced reduction in CO 2 to CO and water.…”

“… 10 − 22 In recent years, however, a number of catalysts with first-row transition-metal elements such as iron or manganese have been identified. 23 − 31 Particularly promising CO 2 reduction catalysts contain an iron(I) porphyrinate group. 32 , 33 Thus, Chang et al took an iron(I) tetraphenylporphyrin (TPP) complex and inserted substituents on the ortho and para positions of one of the phenyl groups ( Scheme 1 ).…”

Porphyrins—valuable pigments of life

“…On account of their substantial absorption in the visible region (400-450 nm Soret band, and 500-700 nm Q-bands) (Kim et al, 2008), as well as their ability to act as electron/energy donors/ acceptors, porphyrins have been examined as artificial photosynthetic mimics (Bottari et al, 2012) and utilized in various solar cell technologies (Urbani et al, 2014;Zeng et al, 2020;Piradi et al, 2021;Molina et al, 2023). In addition, porphyrins (particularly metalloporphyrins), are considered as one of the most effective class of biomimetic catalysts (both in photo-and electrocatalysis), due to their significant catalytic activity in a great variety of chemical processes (Lin et al, 2021;Huang et al, 2022;Nikoloudakis et al, 2022;O'Neill et al, 2022;Domingo-Tafalla et al, 2023). Because of their tuneable optoelectronic properties, porphyrins are also used in molecular recognition and metal-ion sensing applications (Ogoshi and Mizutani, 1999;Ishizuka et al, 2022).…”

Contemporary Strategies for Immobilizing Metallophthalocyanines for Electrochemical Transformations of Carbon Dioxide

“…We choose not to make an extensive list of performance metrics because there is not yet an accepted standard by which to benchmark disparate systems. There are examples of other recent reviews that tabulate such metrics [5,[9][10][11], but doing so is a known challenge in related areas of electrocatalysis [12][13][14][15][16]. Instead, we try to focus on recent approaches to making molecules and materials that have favorable CO 2 reduction kinetics and/or overpotentials.…”