In‐Situ‐Formed Potassium‐Modified Nickel‐Zinc Carbide Boosts Production of Higher Alcohols beyond CH4 in CO2 Hydrogenation

Ni-based catalysts have been widely studied in the hydrogenation of CO₂ to CH₄ , but selective and efficient synthesis of higher alcohols (C₂₊ OH) from CO₂ hydrogenation over Ni-based catalyst is still challenging due to successive hydrogenation of C1 intermediates leading to methanation. Herein, we report an unprecedented synthesis of C₂₊ OH from CO₂ hydrogenation over K-modified Ni-Zn bimetal catalyst with promising activity and selectivity. Systematic experiments (including XRD, in situ spectroscopic characterization) and computational studies reveal the in situ generation of an active K-modified Ni-Zn carbide (K-Ni₃ Zn₁ C_0.7 ) by carburization of Zn-incorporated Ni⁰ , which can significantly enhance CO₂ adsorption and the surface coverage of alkyl intermediates, and boost the C-C coupling to C₂₊ OH rather than conventional CH₄ . This work opens a new catalytic avenue toward CO₂ hydrogenation to C₂₊ OH, and also provides an insightful example for the rational design of selective and efficient Ni-based catalysts for CO₂ hydrogenation to multiple carbon products.