Photocatalytic CO2 Reduction by Near‐Infrared‐Light (1200 nm) Irradiation and a Ruthenium‐Intercalated NiAl‐Layered Double Hydroxide

Near‐infrared light‐driven photocatalytic CO2 reduction (NIR‐CO2PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO2 with low energy NIR photons remains challenging. Herein, a novel NIR‐driven photocatalyst comprising an anionic Ru complex intercalated between NiAl‐layered double hydroxide nanosheets (NiAl‐Ru‐LDH) is shown to deliver efficient CO2 photoreduction (0.887 μmol h−1) with CO selectivity of 84.81% under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression‐related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light‐induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO2PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO2 molecules and lowers the energy barriers for NIR‐CO2PR to CO. To our knowledge, this is one of the first reports of NIR‐CO2PR at wavelengths up to 1200 nm in LDH‐based photocatalyst systems.