Dual Porphyrin Sensitized Photocatalytic System for Visible‐Light‐Driven CO₂ Reduction
Abstract
Dye‐sensitized photocatalysis offers a powerful strategy for combining the molecular selectivity of transition‐metal catalysts with the robustness and charge‐separation capabilities of semiconductor materials. Herein, we report a dual porphyrin–sensitized TiO₂ platform for visible‐light‐driven CO₂ reduction, integrating a Zn‐porphyrin photosensitizer with newly designed Fe‐porphyrin catalysts bearing urea‐based secondary‐sphere functionalities. These hydrogen‐bonding motifs promote CO₂ preorganization and stabilization of key reduced intermediates at the metal center. Systematic comparison of homogeneous and heterogeneous systems reveals a pronounced enhancement in activity and durability upon immobilization onto TiO₂ nanoparticles. Optimization studies demonstrate that catalytic activity is strongly governed by both sacrificial electron donor (SED) availability and proton concentration. Under anhydrous conditions, increased SED concentration boosts turnover numbers, while the introduction of controlled amounts of water enhances proton‐coupled electron transfer but ultimately compromises catalyst stability at higher concentrations. Under optimized conditions, the best‐performing assembly achieves turnover numbers (TONs) exceeding 15,000 after 96 h of irradiation, representing, to the best of our knowledge, the highest reported TON for Fe‐porphyrin‐based dye‐sensitized photocatalytic systems (DSPs). These findings highlight the delicate balance between electron and proton management in dye‐sensitized architectures and provide key design principles for developing durable and efficient molecular–semiconductor hybrids for solar‐driven CO₂ conversion.
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BibTeX
@article{katsari2026dual,
title = {{Dual Porphyrin Sensitized Photocatalytic System for Visible‐Light‐Driven CO₂ Reduction}},
author = {Anna Katsari and Emmanouil Nikoloudakis and Georgios Charalambidis and Antonios Iliakis and Fabrice Odobel and Emmanuel Stratakis},
journal = {ChemSusChem},
year = {2026},
month = oct,
doi = {10.1002/cssc.71128},
url = {https://hal.science/hal-05841307v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Dual Porphyrin Sensitized Photocatalytic System for Visible‐Light‐Driven CO₂ Reduction
AU - Anna Katsari
AU - Emmanouil Nikoloudakis
AU - Georgios Charalambidis
AU - Antonios Iliakis
AU - Fabrice Odobel
AU - Emmanuel Stratakis
PY - 2026
DA - 2026/10/27
JO - ChemSusChem
DO - 10.1002/cssc.71128
UR - https://hal.science/hal-05841307v1
AB - Dye‐sensitized photocatalysis offers a powerful strategy for combining the molecular selectivity of transition‐metal catalysts with the robustness and charge‐separation capabilities of semiconductor materials. Herein, we report a dual porphyrin–sensitized TiO₂ platform for visible‐light‐driven CO₂ reduction, integrating a Zn‐porphyrin photosensitizer with newly designed Fe‐porphyrin catalysts bearing urea‐based secondary‐sphere functionalities. These hydrogen‐bonding motifs promote CO₂ preorganization and stabilization of key reduced intermediates at the metal center. Systematic comparison of homogeneous and heterogeneous systems reveals a pronounced enhancement in activity and durability upon immobilization onto TiO₂ nanoparticles. Optimization studies demonstrate that catalytic activity is strongly governed by both sacrificial electron donor (SED) availability and proton concentration. Under anhydrous conditions, increased SED concentration boosts turnover numbers, while the introduction of controlled amounts of water enhances proton‐coupled electron transfer but ultimately compromises catalyst stability at higher concentrations. Under optimized conditions, the best‐performing assembly achieves turnover numbers (TONs) exceeding 15,000 after 96 h of irradiation, representing, to the best of our knowledge, the highest reported TON for Fe‐porphyrin‐based dye‐sensitized photocatalytic systems (DSPs). These findings highlight the delicate balance between electron and proton management in dye‐sensitized architectures and provide key design principles for developing durable and efficient molecular–semiconductor hybrids for solar‐driven CO₂ conversion.
SN - 1864-5631
SN - 1864-564X
ER -