Exceptional CO <sub>2</sub> Hydrogenation to Ethanol via Precise Single‐Atom Ir Deposition on Functional P Islands
Lingyue Liu, Jinjie Liu, Guangchao Li, Xiuwen Shi, Jun Yin, Shourong Zheng, Ka‐Fu Yung, Hong Bin Yang, Tsz Woon Benedict Lo
Abstract
Abstract The thermocatalytic hydrogenation of CO 2 to ethanol has attracted significant interest because ethanol offers ease of transport and substantial value in chemical synthesis. Here, we present a state‐of‐the‐art catalyst for the CO 2 hydrogenation to ethanol achieved by precisely depositing single‐atom Ir species on P cluster islands situated on the In 2 O 3 nanosheets. The Ir 1 ‐P x /In 2 O 3 catalyst achieves an impressive ethanol yield of 3.33 mmol g −1 h −1 and a turnover frequency (TOF) of 914 h −1 under 1.0 MPa (H 2 /CO 2 =3 : 1) at 180 °C, nearly 8 times higher than that of the unmodified Ir 1 /In 2 O 3 catalyst. Additionally, at a more industrially relevant pressure of 5.0 MPa, the TOF of the Ir 1 ‐P x /In 2 O 3 catalyst can reach up to 2108 h −1 , surpassing previously reported catalysts. Combined in situ characterization and theoretical studies reveal that the hydrogenation process is significantly enhanced by the Ir 1 ‐P x entities. Specifically, the Ir atom facilitates CO 2 activation and C−C coupling, while the surrounding P island exhibits exceptional H 2 dissociation ability. These three steps have been found crucial for the CO 2 hydrogenation reaction. This discovery opens new opportunities for the regulation of the microenvironment of current catalysts by providing essential chemical functionalities that enhance intricate and complex reaction processes.