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Zn‐based catalysts hold great potential to replace the noble metal‐based ones for CO2 reduction reaction (CO2RR). Undercoordinated Zn (Znδ+) sites may serve as the active sites for enhanced CO production by optimizing the binding energy of *COOH intermediates. However, there is relatively less exploration into the dynamic evolution and stability of Znδ+ sites during CO2 reduction process. Herein, we present ZnO, Znδ+/ZnO and Zn as catalysts by varying the applied reduction potential. Theoretical studies reveal that Znδ+ sites could suppress HER and HCOOH production to induce CO generation. And Znδ+/ZnO presents the highest CO selectivity (FECO 70.9 % at −1.48 V vs. RHE) compared to Zn and ZnO. Furthermore, we propose a CeO2 nanotube with confinement effect and Ce3+/Ce4+ redox to stabilize Znδ+ species. The hollow core–shell structure of the Znδ+/ZnO/CeO2 catalyst enables to extremely expose electrochemically active area while maintaining the Znδ+ sites with long‐time stability. Certainly, the target catalyst affords a FECO of 76.9 % at −1.08 V vs. RHE and no significant decay of CO selectivity in excess of 18 h. [ABSTRACT FROM AUTHOR]

Herein, we report highly efficient carbon supported Ni−MoO2 heterostructured catalysts for the electrochemical hydrogenation (ECH) of phenol in 0.10 M aqueous sulfuric acid (pH 0.7) at 60 °C. Highest yields for cyclohexanol and cyclohexanone of 95 % and 86 % with faradaic efficiencies of ∼50 % are obtained with catalysts bearing high and low densities of oxygen vacancy (Ov) sites, respectively. In situ diffuse reflectance infrared spectroscopy and density functional theory calculations reveal that the enhanced phenol adsorption strength is responsible for the superior catalytic efficiency. Furthermore, 1‐cyclohexene‐1‐ol is an important intermediate. Its hydrogenation route and hence the final product are affected by the Ov density. This work opens a promising avenue to the rational design of advanced electrocatalysts for the upgrading of phenolic compounds. [ABSTRACT FROM AUTHOR]