Organic chemistry

Combinatorial chemistry

Catalysis

Inorganic chemistry

Chemistry

Chromophore

Materials science

Metalation

Porphyrin

Redox

Photochemistry

Angewandte Chemie International Edition

In natural photosynthesis, the architecture of multiproteins integrates more chromophores than redox centers and simultaneously creates a well-controlled environment around the active site. Herein, we demonstrate that these features can be emulated in a prototype hydrogen-bonded organic framework (HOF) through simply varying the proportion of metalated porphyrin in the structure. Further studies demonstrate that changing the metalloporphyrin content not only realizes a fine tuning of the photosensitizer/catalyst ratio, but also alters the microenvironment surrounding the active site and the charge separation efficiency. As a result, the obtained material achieves the challenging overall CO2 reduction with a high HCOOH production rate (29.8 μmol g-1 h-1 , scavenger free), standing out from existing competitors. This work unveils that the degree of metalation is vital to the catalytic activity of the porphryinic framework, presenting as a new strategy to optimize the performance of heterogeneous catalysts.

Partial Metalation of Porphyrin Moieties in Hydrogen‐Bonded Organic Frameworks Provides Enhanced CO<sub>2</sub> Photoreduction Activity

Partial Metalation of Porphyrin Moieties in Hydrogen‐Bonded Organic Frameworks Provides Enhanced CO2 Photoreduction Activity

Partial Metalation of Porphyrin Moieties in Hydrogen‐Bonded Organic Frameworks Provides Enhanced CO₂ Photoreduction Activity