Homogeneous Molecular Iron Catalysts for Direct Photocatalytic Conversion of Formic Acid to Syngas (CO+H₂ )

The catalytic decomposition of formic acid to generate syngas (a mixture of H₂ and CO) is a highly valuable strategy for energy conversion. Syngas can be used directly in internal combustion engines or can be converted to liquid fuels, meeting future energy challenges in a sustainable manner. Herein, we report the use of homogeneous molecular iron catalysts combined with a CdS nanorods (NRs) semiconductor to construct a highly efficient photocatalytic system for direct conversion of formic acid to syngas at room temperature and atmospheric pressure. Under optimal conditions, the photocatalytic system presents an activity of 150 mmol g_catalyst ^-1 h^-1 towards H₂ , and an apparent quantum yield (AQY) of 16.8 %, making it among the most active noble-metal-free photocatalytic systems for H₂ evolution from formic acid under visible light. Meanwhile, these iron-based molecular catalysts also demonstrate remarkable enhancement in CO evolution with robust stability. The mechanistic role of the molecular catalyst is further investigated by using cyclic voltammetry, which suggests the formation of Fe^I species as the key step in the catalytic conversion of formic acid to syngas.