Photocatalytic Hydrogen Production with Conjugated Polymers as Photosensitizers

Artificial photosynthesis is a chemical process that aims to capture energy from sunlight to produce solar fuels. Light absorption by a robust and efficient photosensitizer is one of the key steps in solar energy conversion. However, common photosensitizers, including [Ru­(bpy)₃]²⁺ (RuP), remain far from the ideal. In this work, we exploited the performance of conjugated polymers (CPs) as photosensitizers in photodriven hydrogen evolution in aqueous solution (pH 6). Interestingly, CPs, such as poly­(fluorene-<i>co</i>-phenylene) derivative (429 mmol_H₂·g_CP^–1·h^–1), exhibit steady and high reactivity toward hydrogen evolution; this performance can rival that of a phosphonated RuP under the same conditions, indicating that CPs are promising metal-free photosensitizers for future applications in photocatalysis

Redox-Active Ligand Assisted Multielectron Catalysis: A Case of Electrocatalyzed CO₂‑to-CO Conversion

The selective reduction of carbon dioxide remains a significant challenge due to the complex multielectron/proton transfer process, which results in a high kinetic barrier and the production of diverse products. Inspired by the electrostatic and H-bonding interactions observed in the second sphere of the [NiFe]-CODH enzyme, researchers have extensively explored these interactions to regulate proton transfer, stabilize intermediates, and ultimately improve the performance of catalytic CO2 reduction. In this work, a series of cobalt(II) tetraphenylporphyrins with varying numbers of redox-active nitro groups were synthesized and evaluated as CO2 reduction electrocatalysts. Analyses of the redox properties of these complexes revealed a consistent relationship between the number of nitro groups and the corresponding accepted electron number of the ligand at −1.59 V vs. Fc+/0. Among the catalysts tested, TNPPCo with four nitro groups exhibited the most efficient catalytic activity with a turnover frequency of 4.9 × 104 s–1 and a catalytic onset potential 820 mV more positive than that of the parent TPPCo. Furthermore, the turnover frequencies of the catalysts increased with a higher number of nitro groups. These results demonstrate the promising design strategy of incorporating multielectron redox-active ligands into CO2 reduction catalysts to enhance catalytic performance