Induced C−C Coupling by Amorphous‐Crystalline Hybrid Structure for Selective CO₂ Photoreduction into C₂ Fuels

Abstract Selective photoreduction of carbon dioxide (CO 2 ) into high‐value C 2 products remains a formidable challenge due to the elusive C−C coupling step. Herein, the novel concept is first introduced that an amorphous‐crystalline hybrid structure can galvanize previously inert metal atoms, thereby establishing highly active dual sites. This ingenious configuration promotes the C−C coupling, paving the way for CO 2 photoreduction into C 2 products. Taking the Bi 2 MoO 6 nanosheets anchored by amorphous FeOOH species as an example, X‐ray photoelectron spectroscopy (XPS) spectra and X‐ray absorption near edge structure spectra and density functional theoretical (DFT) calculations confirm the electron transfer from FeOOH to Bi 2 MoO 6 nanosheets. Thus, the introduction of FeOOH activates the nonoperative Bi sites for the construction of Bi−Mo dual sites, verified by the in situ XPS spectra and DFT calculations. Gibbs free energy calculations revealed the formation energy barrier of C−C coupling is hugely lowed from 3.41 to 0.45 eV thanks to the presence of FeOOH species. Therefore, the FeOOHBi 2 MoO 6 nanosheets are a game changer, delivering the sole liquid product, acetic acid, with an impressive electron selectivity of ≈86.9%. In contrast, the Bi 2 MoO 6 nanosheets lag behind, only capable of producing carbon monoxide from CO 2 photoreduction.